Step coverage using an inhibitor molecule for high aspect ratio structures

1. A method for improving step coverage of a film deposited on high aspect ratio (HAR) apertures in a substrate, the method comprising: i) sequentially or simultaneously exposing the substrate to a vapor of an inhibitor, a vapor of a precursor ZrCp(NMe2)3 and a vapor of a co-reactant; and ii) allowing the film with a desired step coverage being deposited on the surface of the HAR apertures through a vapor deposition process, wherein the inhibitor is selected from one or more of a) phosphorus based aliphatic and aromatic inhibitors; b) boron based aliphatic and aromatic inhibitors; c) H2O vapor, H2 gas, CO gas, CS gas and nitrogen oxide (NOx) gases; and d) combinations of a)-c).

2. The method of claim 1, further comprising maintaining a temperature of the substrate in a range of from room temperature to 650° C.

3. The method of claim 1, wherein the inhibitor is selected from one or more of a. diols, ethers, epoxides, aldehydes, ketones, carboxylic acids, enols, esters, anhydrides, phenols, substituted phenols; b. amines, imines, imides, azides, cyanates, nitrile, nitrate, nitrite, nitrogen containing heterocycles; c. thiols, sulfides, disulfide, sulfonxide, thiocyanates, isothiocyanates, thioesters; d. phosphines, phosphonic acid, phosphodiesters; e. boronic acid, boronic ester, borinic esters; carbon based aliphatic inhibitors including alkanes, alkenes, alkynes and benzene derivatives; f. I2; g. or combinations of a)-f).

4. The method of claim 3, wherein the inhibitor is a radical form of a vapor or gas of the inhibitor at a temperature ranging from room temperature to approximately 650° C. generated with or without plasma.

5. The method of claim 1, wherein the co-reactant is O3, O2, H2O, H2O2, D2O, alcohols, NH3, N2, N2H2, H2, or radicals thereof generated by plasma.

6. The method of claim 1, wherein the co-reactant is O3 or O3 radicals generated by plasma.

7. The method of claim 1, wherein the desired step coverage is ≥100%.

8. The method of claim 1, wherein the desired step coverage is larger than the step coverage with the absence of the inhibitor.

9. The method of claim 1, wherein the HAR ranges from 25:1 to 200:1.

10. The method of claim 1, wherein the substrate is a patterned or 3D structure.

11. The method of claim 1, wherein the aperture is a hole, a via, a trench, a gap or an opening formed in the substrate from a previous manufacturing step.

12. The method of claim 1, wherein the vapor deposition process is ALD, CVD or combination thereof.

13. The method of claim 1, wherein the vapor deposition process is a plasma enhanced CVD selected from a spatial ALD, a thermal ALD, or a plasma enhanced ALD.

14. The method of claim 1, wherein an order of exposing the substrate to the inhibitor, the precursor and the co-reactant includes i) the inhibitor, the precursor and the co-reactant sequentially; ii) the precursor, the inhibitor and the co-reactant sequentially; iii) the precursor, the co-reactant and the inhibitor sequentially; or iv) the inhibitor and the precursor simultaneously and then the co-reactant.

15. The method of claim 14, further comprising purging and removing one or more of an excess inhibitor, an excess precursor and an excess co-reactant after each exposure using a purge gas, wherein the purge gas is an inert gas selected from N2, Ar, Kr or combinations thereof.